CN105032471B - A kind of visible light-responded nano-TiO2The preparation of/Zeolite composite materials - Google Patents
A kind of visible light-responded nano-TiO2The preparation of/Zeolite composite materials Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 54
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 50
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910010298 TiOSO4 Inorganic materials 0.000 claims abstract description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 16
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- 230000008569 process Effects 0.000 claims description 8
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- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 4
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- 238000010521 absorption reaction Methods 0.000 claims description 2
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- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000001802 infusion Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000002835 absorbance Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
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- 239000000243 solution Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 20
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
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- 230000001699 photocatalysis Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
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- 235000010215 titanium dioxide Nutrition 0.000 description 3
- 229910010416 TiO(OH)2 Inorganic materials 0.000 description 2
- -1 Titanium alkoxides Chemical class 0.000 description 2
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- 229910001456 vanadium ion Inorganic materials 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of visible light-responded nano-TiO2/ Zeolite composite materials and preparation method, wherein zeolite are sheet-like particle, and particle size distribution is 10 100 μm；Nano-TiO2Mean particle size is 10 14nm, and crystal formation is Detitanium-ore-type；The doping of S elements improves TiO2Visible light catalysis activity.The composite is with TiOSO4For titanium source, using urea as precipitating reagent, nano-TiO is made using sluggish precipitation2Presoma, then calcine the doping for realizing S elements by impregnating.Visible light-responded nano-TiO prepared by the present invention2/ Zeolite composite materials are in the range of 390~500nm of visible ray compared with general T iO2/ Zeolite composite materials absorbance is obviously improved, and preparation technology is simple, easily operation, it is not necessary to which special equipment, investment of production is few, easily realizes industrialized production.
Description
Technical field
The present invention relates to a kind of visible light-responded nano-TiO2The preparation of/Zeolite composite materials, belongs to nonmetallic ore deep
Rapidoprint and TiO2Photocatalysis technology field, product is mainly used in the association areas such as environmental contaminants processing.
Background technology
TiO2, can be with due to having the advantages that oxidability strong, stable chemical performance, cheap and secondary pollution are small
It is CO by organic pollutant degradation2, the inorganic molecules such as water, heavy metal ion is reduced to the low price ion of nonhazardous, degraded
Vehicle exhaust, can also disinfection, be widely used in fields such as environmental protection, catalyst, coating, so being considered as most
Photochemical catalyst with practical prospect；And light-catalyzed reaction has huge application in terms of solar energy conversion and the depollution of environment
Value, it is of great interest in recent years.But, as a kind of n-type semiconductor, its larger band gap causes only ultraviolet
Light could effectively excite its valence-band electrons to transit to conduction band, so the utilization rate to solar energy is only 3-5%, this restrict this
The practical application of item technology.Therefore, research and development one kind can extend TiO2Response wave length make full use of the modification skill of sunshine
Art has become TiO2The one big focus in photocatalysis technology field and have great importance and actual application value.
At present, preparing has visible light-responded nano-TiO2Some the existing researchs of the method for/Zeolite composite materials.See with
Lower bibliography：(1) patent of invention " titanium dioxide antibacterial paper of zeolite-loaded vanadium ion doping and preparation method thereof ", application number
201010519314.4, applicant South China Science ＆ Engineering University；Vanadium ion used belongs to rare metal in this method, uses Titanium alkoxides
It is expensive as titanium source, irritant smell and micro- poison, hydrolysising condition be difficult to control, and pilot process to use it is substantial amounts of
Organic solvent, material cost is high, it is difficult to realize industrialized production.(2) Hou Tianyi, Jiang Yinshan, Li Fangfei, wait .Fe to adulterate and day
Right Zeolite support is to TiO2Influence [J] SCIs of photocatalytic activity, 2006,27 (1):100–103.It is this
TiCl used in method4Easily hydrolyze, and the TiCl of high concentration4Acid mist can be more caused in dilution, not easy to operate, industry
It is serious to equipment corrosion in production, and substantial amounts of organic solvent is used in preparation process, production cost is added, it is uncomfortable
Industrialized production is realized in conjunction.
At present, researchers attempt to extend TiO by technologies such as ion doping, noble metal loading, semiconductors couplings2's
Response wave length.For example, visible light catalysis activity is improved by Prospects of Rare Metal Vanadium and Fe doping in above-mentioned bibliography (1), (2),
But this process for preparing sol-gel and selected titanium source are all difficult to realize industrialized production.
Sluggish precipitation is mainly characterized by with TiOSO4For titanium source, (TiOSO4Cheap, environmental pollution is small, can be with
The waste liquid production in Ti industry in Titanium White Production By Sulfuric Acid Process is comprehensively utilized, is industrialized production nano-TiO2Preferred titanium source),
Urea is heated slow decomposition ammonification as precipitating reagent, using urea and uniformly discharges OH at a certain temperature-Make TiOSO4Hydrolysis is heavy
Form sediment and slowly carry out, gained precipitation is again through the obtained nano-TiO of calcining2Epigranular is fine and close and impure few, its react include with
Under several reactions：
Urea decomposition reaction：(NH4)2CO+3H2O→2NH4OH+CO2
TiOSO4Hydrolytic precipitation reacts：TiOSO4+2NH4OH→TiO(OH)2+(NH4)2SO4
Calcination reaction：TiO(OH)2→TiO2+H2O
S element dopings are selected to improve its photocatalysis performance, the modifying function for there are several aspects:(l) photochemical catalyst is expanded
Photoresponse scope；(2) efficiently separating for light induced electron and photohole is promoted；(3) TiO is changed2Microstructure.Due to mesh
The preceding TiO that adulterated to S2The research of photochemical catalyst is fewer, therefore prepares and research S/TiO2Photochemical catalyst can be by light so that one kind is made
The nano-TiO of response2/ Zeolite composite materials have highly important theoretical research and actual application value.
The content of the invention
For shortcoming present in above-mentioned prior art, the technical problems to be solved by the invention are to provide a kind of visible ray
The excellent nano-TiO using zeolite as carrier of catalytic performance2/ Zeolite composite materials, and it is a kind of suitable for industrialized production
The preparation method of the product.
Therefore, the invention provides a kind of visible light-responded nano-TiO by carrier of zeolite2/ Zeolite composite materials,
Wherein described zeolite is sheet-like particle, and particle size distribution is 10-100 μm；The nano-TiO2Mean particle size is 10-
14nm, crystal formation is anatase；The nano-TiO2Particle the zeolite surface is uniform, fine and close distribution, and the S elements of doping with
S4+Form enters TiO2Replace part Ti in lattice4+, cause distortion of lattice, the absorption that forming oxygen vacancy makes it to light produces red
Move, so as to improve TiO2The catalytic activity of visible ray.
The present invention is first with the porous rack-like design feature of zeolite, with selectivity is strong, adsorptivity is strong, easily reclaim etc.
Advantage, solves the nano-TiO of the suspended state in actual application well2The shortcomings of being difficult to reclaim, be easily poisoned, in addition,
The present invention realizes nano-TiO using sluggish precipitation2Uniform, fine and close distribution of the particle in zeolite surface, it is to avoid nano-TiO2
Accumulation agglomeration between particle, forms one layer of nano-TiO2Film.So cause nano-TiO2Particle has good point
Property is dissipated, the photo-generate electron-hole generated during light-catalyzed reaction is reduced to the compound probability of collision, make more photoproduction electricity
Son-hole is to moving to nano-TiO2Particle surface participates in redox reaction；Moreover, the S of doping is with S4+Form enters TiO2
Replace part Ti in lattice4+, not only reduce nano-TiO2Energy gap so as to extending TiO2Response wave length, and not
Influence nano-TiO2Particle is uniformly distributed zeolite surface so that product has higher visible light catalysis activity, so that
Good actual application value can be obtained under sunshine by obtaining composite.
In addition, heretofore described nano-TiO2The mass percent of particle and the zeolite is 9%-33%；Thiocarbamide with
TiO2Mass ratio be (0.5~1.5)：100.Because the present invention realizes nano-TiO2/ Zeolite composite materials visible light catalytic is lived
The optimum efficiency of property, that is, nano-TiO2With the usage ratio and thiocarbamide and nano-TiO of zeolite2Usage ratio reach most preferably,
So as to can effectively control feeding intake for raw material in preparation process, it is to avoid the waste of raw material, and ensure the stabilization of product quality.
Invention further provides a kind of method for preparing the product, with TiOSO4For titanium source, urea is precipitating reagent,
Nano-TiO is made using sluggish precipitation2Presoma, then the doping for realizing S elements is calcined by impregnating, it is made visible light-responded
Nano-TiO2/ Zeolite composite materials, including following process steps：
(1) compound concentration is 0.1-0.2mol/L TiOSO4Solution, by solid-to-liquid ratio 1:15-25 (solid masses：Liquid bulk
Product, solid masses unit g, liquid volume per unit ml) by zeolite and TiOSO4Solution is mixed, then by TiOSO4:Urea=1:1.5-
2.5 (mol ratios) add urea, then stir；
(2) mixing liquid of gained in above-mentioned steps is heated into 1-3h at a temperature of 70-85 DEG C, is during which stirred continuously, enters
Water-filling solution precipitation reaction；
(3) precipitated product of gained in above-mentioned steps is filtered, while washing off SO with water4 2-Ion, then in 100-
Dried under the conditions of 105 DEG C；
(4) compound concentration is 0.01mol/L thiourea solution, then according to thiocarbamide and TiO2Mass ratio for (0.5~
1.5)：100 add concentration for 0.01mol/L thiourea solution and are mixed with the drying product of step (3), after ultrasonic micro- 5min that shakes
1h is impregnated, is then dried under the conditions of 80 DEG C.
(5) 1- 3h will be calcined at a temperature of 300-450 DEG C after the drying object grinding distribution of gained in above-mentioned steps, most
Described visible light-responded nano-TiO is obtained eventually2/ Zeolite composite materials.
In above-mentioned preparation method, TiOSO4The centre during Titanium White Production By Sulfuric Acid Process in Ti industry can be comprehensively utilized
Waste liquid, and China's zeolite resource is abundant, it is cheap, so material source is wide and cost is low.In addition, above-mentioned steps (4),
(5) there is no sulfurous pollutants generation during, and filtering in above-mentioned steps (3) and flushing waste are acid and contain
SO4 2-Ion, it is possible to use simultaneously CaSO is made in CaO neutralization reactions4, comprehensive utilization is realized, the pollution to environment is reduced.The present invention
Described in product preparation method and technological process it is simple, easily operation, it is not necessary to which special equipment, investment of production is few is easily real
Existing industrialized production.
Brief description of the drawings
Fig. 1 schemes for the SEM of zeolite in the present invention.
Fig. 2 is nano-TiO visible light-responded in the present invention2The SEM figures of/Zeolite composite materials.
Fig. 3 is nano-TiO visible light-responded in the present invention2/ Zeolite composite materials and common nano-TiO2/ zeolite is multiple
Ultraviolet-visible absorption spectroscopy (UV-Vis) comparison diagram of condensation material.
Fig. 4 is nano-TiO visible light-responded in the present invention2/ Zeolite composite materials and common nano-TiO2/ zeolite is multiple
The energy gap comparison diagram of condensation material.
Embodiment
The product of the present invention is further described below in conjunction with the accompanying drawings.
Zeolite shown in Fig. 1 in the present invention is sheet-like particle, and particle size distribution is 10-100 μm.Shown in Fig. 2 originally
Visible light-responded nano-TiO in invention by carrier of zeolite2Nano-TiO in/Zeolite composite materials2It is equal in zeolite surface
Even, fine and close distribution.It is visible light-responded nano-TiO in the present invention shown in Fig. 32/ Zeolite composite materials are in visible ray 390
More common nano-TiO in the range of~500nm2/ Zeolite composite materials absorbance is obviously improved, and shows obvious visible light catalytic
Activity.It is visible light-responded nano-TiO in the present invention shown in Fig. 42The more common nanometer of energy gap of/Zeolite composite materials
TiO2The energy gap of/Zeolite composite materials is substantially reduced, and extends TiO2Response wave length can so as to improve composite
See photocatalytic activity.
The product preparation method of the present invention is further described with reference to specific embodiment.
Implement 1：
Raw material is introduced：Zeolite comes from Guilin, and main chemical compositions and content are SiO259.28%,
Al2O312.05%, CaO9.87%, K2O0.14%, Fe2O30.09%, Na2O0.08%.Titanyl sulfate is chemical pure, Tianjin
Recover fine chemistry industry research institute, white powder, chemical formula TiOSO4·2H2O, containing free H2SO4≤ 8.0%, TiO2Content is many
In 38%；Urea is pure, the Beijing Chemical Plant of analysis, chemical formula (NH2)2CO；Thiocarbamide is pure, the Tianjin Tianjin section fine chemistry industry of analysis
Research institute, chemical formula is H2NCSNH2。
Step of preparation process is as follows：
(1) 0.1mol/L TiOSO is prepared first4Solution.Weigh TiOSO4Powder 19.6g (0.1mol), adds 1000ml
Distilled water, is quickly stirred, solution gradually becomes clarification from milky in temperature is 40-60 DEG C of hot water, i.e., with concentration is
0.1mol/L TiOSO4Solution.
(2) it is 0.1mol/L TiOSO to take zeolite 8g and concentration4Solution 120ml, i.e., by solid-to-liquid ratio 1：15 (solid matter
Amount：Liquid volume, solid masses unit g, liquid volume per unit ml) mixing；TiOSO is pressed again4：Urea=1：2 (mol ratios) add
Enter urea, due to adding TiOSO4For 0.012mol, that is, it is 0.024mol (1.44g) to add urea, and solution is sufficiently stirred for
It is even.
(3) gained mixing liquid in above-mentioned steps is heated into 3h at a temperature of 70 DEG C, during which wants continuous agitating solution, carry out
Hydrolytic precipitation reacts.
(4) precipitated product of gained in above-mentioned steps is filtered, while washing off SO with water4 2-Ion, Zhi Daoyong
0.1mol/L BaCl2Untill solution can't detect white precipitate in filtrate；After the completion of filtering, dried under the conditions of 105 DEG C.
(5) compound concentration is 0.01mol/L thiourea solution, then according to thiocarbamide and TiO2Mass ratio be 0.5：100
6ml concentration is added for 0.01mol/L thiourea solution and is mixed with the drying product of step (4), dipping after the micro- 5min that shakes of ultrasound
1h, is then dried under the conditions of 80 DEG C.
(6) 3h will be calcined at a temperature of 300 DEG C after the drying object grinding distribution of gained in above-mentioned steps, finally giving can
See the nano-TiO of photoresponse2/ Zeolite composite materials.
In addition, it should be noted that due in the present invention concentration be 0.1-0.2mol/L TiOSO4The pH=1- of solution
2, in above-mentioned steps (1) to (4), the equipment and instrument to be used is needed with resistance to acid function.In addition to this restriction, to the neck
It is inessential using which type of apparatus for the technical staff in domain, as long as the purpose to be realized can be reached.
Embodiment 2：
Identical with the raw material and processing step in embodiment 1, difference is following technological parameter： TiOSO4Solution
Concentration 0.1mol/L, zeolite and TiOSO4The solid-to-liquid ratio of solution is 1：25, TiOSO4:Urea=1：2 (mol ratios), hydrolysis is heavy
Form sediment 75 DEG C of temperature and time 2h in reacting, and addition 15ml concentration is 0.01mol/L thiourea solution (according to thiocarbamide and TiO2's
Mass ratio is 0.75：100), 350 DEG C of temperature and time 2h in calcination process.
Embodiment 3：
Identical with the raw material and processing step in embodiment 1, difference is following technological parameter： TiOSO4Solution
Concentration 0.15mol/L, zeolite and TiOSO4The solid-to-liquid ratio of solution is 1：20, TiOSO4:Urea=1：1.5 (mol ratios), water
80 DEG C of temperature and time 2h in precipitation reaction are solved, thiourea solution (thiocarbamide and TiO that 24ml concentration is 0.01mol/L is added2's
Mass ratio 1：100), 400 DEG C of temperature and time 1h in calcination process.
Embodiment 4:
Identical with the raw material and processing step in embodiment 1, difference is following technological parameter： TiOSO4Solution
Concentration 0.2mol/L, zeolite and TiOSO4The solid-to-liquid ratio of solution is 1：20, TiOSO4:Urea=1：2 (mol ratios), hydrolysis is heavy
Form sediment 85 DEG C of temperature and time 1h in reacting, and adds thiourea solution (thiocarbamide and TiO that 40ml concentration is 0.01mol/L2Quality
Than for 1.25：100), 450 DEG C of temperature and time 3h in calcination process.
Method as described below, test and the performance and parameter for calculating final products in embodiment 1 to 4, gained
The results are shown in Table 1.
The test of methylene blue solution degradation rate：Sample is bigger to the degradation rate of methylene blue solution under given conditions,
Illustrate that its photocatalysis performance is better.In present embodiment, the concentration of methylene blue solution used is 10mg/L, light source used
For 500W xenon lamps (simulated solar irradiation), surveyed on the BL-GHX-V type photochemical reaction instrument produced in Shanghai than bright Instrument Ltd.
The photocatalysis performance of trial product.100ml methylene blue solutions and 0.1g product mixes are taken every time, are first stirred under non-illuminated conditions
40min, is well mixed solution.Then turn on light illumination, carry out light-catalyzed reaction.Sampled during illumination 5h with centrifuge tube, through at a high speed
After centrifugation, supernatant is taken to survey absorbance at 666nm wavelength on spectrophotometer, then the degradation rate of methylene blue solution is calculated
Formula is：Degradation rate=(C0- Ct)/C0× 100%, C in formula0For the absorbance of initial methylene blue solution, CtFor illumination 5h
When methylene blue solution absorbance.
Nano-TiO2The measure of mean particle size and crystal formation：XRD points are carried out to product using x-ray powder diffraction instrument
Analysis.Nano-TiO in product can be drawn according to the XRD energy spectrum diagrams of gained2For Detitanium-ore-type.Calculated and received according to Scherrer formula
Rice TiO2The average grain diameter of particle：In D=0.89 λ/β cos θ, formula：D is average grain diameter；λ=0.15406nm；θ is the angle of diffraction；β
For the half-peak breadth of the most strong crystal face of characteristic diffraction peak 101 of anatase.
Nano-TiO2Photochemical catalyst energy gap value Eg calculating：Utilize [F (R) hv]1/2Figure is done to hv, line part is utilized
Abscissa intersection point, as energy gap value are exceptionally pushed into, A (Absorbance) is the absorbance in UV-vis DRS.
The performance and parameter of final products in the embodiment 1 to 4 of table 1
| Product | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| The degradation rate (%) of methylene blue solution | 83.43 | 87.29 | 79.92 | 68.21 |
| Nano-TiO2The average grain diameter (nm) of particle | 12.13 | 11.32 | 12.87 | 13.25 |
| Nano-TiO2Crystal formation | Anatase | Anatase | Anatase | Anatase |
| Nano-TiO2Energy gap value Eg | 2.34 | 2.32 | 2.57 | 2.80 |
Although finally it should be noted that the present invention is described in detail above in conjunction with the embodiments, affiliated skill
The technical staff in art field is it is understood that on the premise of present inventive concept is not departed from, in claims, may be used also
To carry out alterations and modifications etc. to above-described embodiment.
Claims (1)
1. a kind of visible light-responded nano-TiO prepared by carrier of zeolite2The method of/Zeolite composite materials, with TiOSO4For
Titanium source, using urea as precipitating reagent, using thiocarbamide as doping sulphur source, visible light-responded nanometer is made using homogeneous precipitation infusion process
TiO2/ Zeolite composite materials, including following process steps：
(1) compound concentration is 0.1~0.2mol/L TiOSO4Solution, by solid-to-liquid ratio 1g：(15~25) mL is by zeolite and TiOSO4
Solution is mixed, then by TiOSO4Mol ratio with urea is 1:1.5~2 add urea, then stir；
(2) mixing liquid of gained in above-mentioned steps is heated into 1~3h at a temperature of 70-85 DEG C, is during which stirred continuously, enters water-filling
Solve precipitation reaction；
(3) precipitated product of gained in above-mentioned steps is filtered, while washing off SO with water4 2-Ion, then 100~105
Dried under the conditions of DEG C；
(4) compound concentration is 0.01mol/L thiourea solution, then according to thiocarbamide and TiO2Mass ratio be (0.5~1.5)：
100 add concentration for 0.01mol/L thiourea solution and are mixed with the drying product of step (3), dipping after the micro- 5min that shakes of ultrasound
1h, is then dried under the conditions of 80 DEG C；
(5) 1~3h will be calcined in above-mentioned steps after the drying object grinding distribution of gained at a temperature of 300~450 DEG C, it is final to obtain
To described visible light-responded nano-TiO2/ Zeolite composite materials；
The zeolite is sheet-like particle, and particle size distribution is 10~100 μm；The nano-TiO2Mean particle size be 10~
14nm, crystal formation is anatase；The nano-TiO2Particle is the zeolite surface is uniform, fine and close distribution, no accumulation agglomeration
Produce, form one layer of nano-TiO2Film；The S elements of the doping are with S4+Form enters TiO2Replace part Ti in lattice4+,
Cause distortion of lattice, the absorption that forming oxygen vacancy makes it to light produces red shift.
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